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Resonant microstrings show promise as a new analytical tool for thermal characterization of polymers with only few nanograms of sample. The detection of the glass transition temperature (Tg) of an amorphous poly(d,l-lactide) (PDLLA) and a semicrystalline poly(l-lactide) (PLLA) is investigated. The polymers are spray coated on one side of the resonating microstrings. The resonance frequency and quality factor (Q) are measured simultaneously as a function of temperature. Change in the resonance frequency reflects a change in static tensile stress, which yields information about the Young’s modulus of the polymer, and a change in Q reflects the change in damping of the polymer-coated string. The frequency response of the microstring is validated with an analytical model. From the frequency independent tensile stress change, static Tg values of 40.6 and 57.6 °C were measured for PDLLA and PLLA, respectively. The frequency-dependent damping from Q indicates higher Tg values of 62.6 and 88.8 °C for PDLLA and PL...

Today's consumer electronics are made from nonrenewable and toxic components. They are also rigid, bulky, and manufactured in an energy-inefficient manner via CO2-generating routes. Though petroleum-based polymers such as polyethylene terephthalate and polyethylene naphthalate can address the rigidity issue, they have a large carbon footprint and generate harmful waste. Scalable routes for manufacturing electronics that are both flexible and ecofriendly (Fleco) could address the challenges in the field. Ideally, such substrates must incorporate into electronics without compromising device performance. In this work, we demonstrate that a new type of wood-based [nanocellulose (NC)] material made via nanosilicate (NS) reinforcement can yield flexible electronics that can bend and roll without loss of electrical function. Specifically, the NSs interact electrostatically with NC to reinforce thermal and mechanical properties. For instance, films containing 34 wt % of NS displayed an increased young's modulus (1.5 times), thermal stability (290 → 310 °C), and a low coefficient of thermal expansion (40 ppm/K). These films can also easily be separated and renewed into new devices through simple and low-energy processes. Moreover, we used very cheap and environmentally friendly NC from American Value Added Pulping (AVAP) technology, American Process, and therefore, the manufacturing cost of our NS-reinforced NC paper is much cheaper ($0.016 per dm-2) than that of conventional NC-based substrates. Looking forward, the methodology highlighted herein is highly attractive as it can unlock the secrets of Fleco electronics and transform otherwise bulky, rigid, and "difficult-to-process" rigid circuits into more aesthetic and flexible ones while simultaneously bringing relief to an already-overburdened ecosystem.

Functional 3D components such as perfusion channels and mechanical actuation elements at cellular length scales can support cell survival and tissue maturation in tissue modeling devices. These advanced requirements call for increasingly complex materials and 3D fabrication methods. Here, a high-resolution dual-material 3D printing concept is developed, where distinct materials are produced locally by orthogonal chemical reactions depending on the illumination wavelength. A tough, stiff epoxy network results from cationic polymerization in UV light, while a soft and diffusion-open hydrogel forms by free-radical polymerization initiated by blue light. Thus, dual-exposure allows for selection of material properties in every voxel, while retaining the 3D design flexibility associated with stereolithography. This enables single-process fabrication of devices integrating mechanically stable chip-to-world interconnects and compliant, diffusion-open perfusable channel components of 150 µm in width and height, while also allowing structural and mechanical feature dimensions down to 60 µm. A perfusion chip capable of creating a stable uniaxial chemical gradient by passive dye diffusion through hydrogel sections, and a negative Poisson ratio structure based on the interplay between stiff rotators and compliant hinges, are manufactured as proof-of-concept microdevices. Lastly, week-long culture of hydrogel-encapsulated human liver cells demonstrates the cytocompatibility of both materials.

We present structural relaxation studies of a polystyrene star polymer after cessation of high-rate extensional flow. During the steady-state flow, the scattering pattern shows two sets of independent correlations peaks, reflecting the structure of a polymer confined in a fully oriented three-armed tube. Upon cessation of flow, the relaxation constitutes three distinct regimes. In a first regime, the perpendicular correlation peaks disappear, signifying disruption of the virtual tube. In a second regime, broad scattering arcs emerge, reflecting relaxation from highly aligned chains to more relaxed, still anisotropic form. New entanglements dominate the last relaxation regime where the scattering pattern evolves to a successively elliptical and circular pattern, reflecting relaxation via reptation.

Reanalysis of an asymmetric poly(ethylene-alt-propylene)-block-polydimethylsiloxane (PEP-PDMS) diblock copolymer first investigated in 1999 has revealed a rich phase behavior including a dodecagonal quasicrystal (DDQC), a Frank-Kasper σ phase, and a body-centered cubic (BCC) packing at high temperature adjacent to the disordered state. On subjecting the sample to large amplitude oscillatory shear well below the σ-BCC order-order transition temperature (TOOT), small-angle X-ray scattering evidenced the emergence of a twinned BCC phase that, on heating, underwent a phase transition to an unusually anisotropic DDQC state. Surprisingly, we observe no evidence of this apparent epitaxy on heating or cooling through the equilibrium σ-BCC transition. We rationalize these results in terms of a shear-induced order-order transition and an apparent BCC-DDQC epitaxy favored by micelle translation-mediated ordering dynamics far below TOOT.

We study the relaxation of linear polymer molecules following fast uniaxial extension. Polystyrene melts of M-w = 80 kg/mol are elongated at a Rouse-Weissenberg number W-iR = 1.5 to Hencky strain epsilon = 3, where steady state is approached using a filament stretch rheometer. Samples were quenched for different duration of stress relaxation at constant Hencky strain to preserve molecular conformation by rapid cooling below the glass transition temperature. Expansion of ex situ small-angle neutron-scattering data in spherical harmonics shows experimental evidence for the decoupling of local and global relaxation phenomena from highly stretched states. This work demonstrates both that the decoupling can be seen in the spherical harmonics expansion and that it can be seen even for short chains provided the initial state is highly oriented.

The intravaginal route of administration can be exploited to treat local diseases and for systemic delivery. In this work, we developed an alginate/chitosan membrane sufficiently stable in a simulated vaginal fluid and able to dissolve over time at a very slow and linear rate. The membrane demonstrated good mechanical properties both in its swollen and dry form. As a study case, we evaluated the viability of this potential drug delivery system for the treatment of bacterial vaginosis, a common disease affecting women in their reproductive age. Metronidazole was effectively included in the alginate/chitosan membrane and its bactericide effect was demonstrated against Staphylococcus aureus and Gardnerella vaginalis, simultaneously showing good biocompatibility with a cervix epithelial cell line. Since this alginate/chitosan membrane is stable in a simulated vaginal environment, is easy to fabricate and can be used for the controlled release of a model drug, it represents a promising drug delivery system for local intravaginal applications.

Nanoporous zirconia with high surface area and crystallinity has a wide range of industrial applications, such as in inorganic exchangers for ion exchange columns, catalyst substrates, and packing material for HPLC. Spherical particles of crystalline nanoporous zirconia are highly desired in various industries due to easy handling of the materials in a fluidized bed. Here, spray drying was adopted to produce spherical nanoporous zirconia powders in both laboratory scale and pilot plant scale. Effect of salts on spray-dried ZrO2 powders and their crystallization behavior was studied. It was found that addition of salts to the zirconia precursors has a huge effect on the crystallization of nanoporous zirconia powders. These results have a great impact on the development of microspheres of nanocrystalline ZrO2 and potentially open up a new opportunity to the low-cost production of porous ceramic microspheres with the salt templating method, in general.

Fundamental understanding of microphase separation in ABC miktoarm copolymers is vital to access a plethora of nonconventional morphologies. Miktoarm stars based on poly(cis 1,4-isoprene) (I), poly(styrene) (S), and poly(2-vinylpyridine) (V) are model systems, which allow systematic studies of the effects of composition, chemical microstructure, and temperature on the thermodynamics of microphase separation. Eleven ISV-x (I:S:V = 1:1:x, v:v:v) miktoarm copolymers were synthesized by anionic polymerization affording well-defined copolymers with a variable V arm. Equilibrium bulk morphologies of all samples, as evidenced by smallangle X-ray scattering, transmission electron microscopy (TEM), and self-consistent field theory, showed a systematic transition from lamellae (x ≈ 0–0.2) to [8.8.4] tiling (x ≈ 0.6–0.9) to cylinders inundulating lamellae (x ≈ 2–4) and, finally, to hexagonally packed core–shell cylinders (x ≈ 5–8). Chemical microstructure of the I arm [poly(cis 1,4-isoprene)] versus poly(3,4-isoprene) is shown to play important role in affecting morphological behavior. To reconcile differences between ISV-x star morphologies reported in the literature and those reported herein, even for the same composition, effects of the microstructure of I arm on the Flory–Huggins parameter between I and V arms were taken into account in a qualitative manner.

The interfacial shear strength (IFSS) is commonly used for evaluating the adhesion at the interface between fibre and matrix. A glass fibre/epoxy matrix system was investigated. The surface coatings applied to glass fibres may result in a discrepancy in the amine:epoxide group ratio between the interface and the bulk matrix, consequently moving the ratio away from the optimum stoichiometric ratio most often used. The amine:epoxide group ratio in the matrix was varied to obtain the optimum ratio at the interface. The study found that the amine:epoxide ratio influenced the IFSS with an optimum just below the stoichiometric ratio. The microbond test was conducted in a thermal mechanical analyser (TMA) to determine the IFSS thus revealing an inverse dependency on the testing temperature: an increased testing temperature yields a decrease of IFSS. IFSS determined at temperatures below the glass transition temperature displays a decreasing trend at high amine:epoxide ratio whereas IFSS measured at testing temperatures above the glass transition temperature steadily increases as the amine:epoxide ratio increases. The microbond test was conducted using both a tensile tester and a TMA setup. The two microbond test setups yielded results with same behaviour of the IFSS as a function of the amine:epoxide ratio.

By combining poly(1,4-isoprene) (PI) with poly(ferrocenylmethyl methacrylate) (PFMMA) in a diblock copolymer structure by means of anionic polymerization we obtained narrowly dispersed PI-b-PFMMA copolymers with molecular weight ranging from 13000 to 62000 g/mol. The products were stable up to 228 °C, according to thermal gravimetry, which allowed us to further investigate their viscoelastic and X-ray scattering properties at elevated temperature by rheology and SAXS, respectively. For PI-b-PFMMA with total molecular weight 13400 g/mol a phase transition at 105 °C was identified leading to the segmental mixing at T > 105 °C and microphase separation at T

In a quest for renewable and highly efficient energy storage devices, carbonaceous hydrogels obtained from biopolymers have received much attention owing to their multifunctional properties [1]. The ability to fine-tune the structures of these hydrogels and the prospects of fabricating 3D hydrogels-based carbon electrodes with highly porous and interconnected nanostructure is believed to provide efficient migration of electrolyte ions and electrons. Even though additive manufacturing (AM) of hydrogels with 3D structures could simplify the fabrication, the printability of each material varies greatly. Furthermore, the mechanical properties of hydrogels are often too weak to withstand the printing of structures with a certain height [2]. Herein, we demonstrate a facile and versatile method for the fabrication of novel and highly porous 3D carbon aerogel electrodes from bio-hydrogels based on additive manufacturing assisted solvent casting process followed by freeze drying and pyrolysis. Firstly, the negative templates with the required resolution and geometry were 3D printed using high-resolution stereolithography (SLA) based AM technology to be used as master molds and the pattern were transferred to the biopolymeric hydrogels during ionic crosslinking induced self-assembly, leading to gelation. After completion of the gelling process, the casted hydrogel was removed from the master mold, washed with deionized water, frozen using solid carbon dioxide (dry ice) and lyophilized (freeze-dried) to preserve the structure. The lyophilized free-standing aerogels were then converted to free-standing 3D pyrolytic carbon aerogels in a high-temperature tubular furnace at 900°C under a nitrogen environment. Different characterization techniques such as FTIR, BET, SEM, Raman, XRD and XPS were employed to access the influence of the process parameters on the final microstructure of the 3D carbon aerogels. The as-prepared 3D free-standing carbon aerogel when used as a binder-free electrode showed outstanding charge storage capability and kinetics arising from interconnected 3D porous channels. The versatility of this approach was further verified by the successful preparation of novel multifunctional 3D free-standing carbon aerogel hybrids using GO, CNT and/or metal oxides and its application as a structured binder-free supercapacitor electrode with improved electrochemical performance. With the advantageous features of synergistically regulating the structure and composition, the proposed method combining AM and casting could be used as a versatile tool to develop structured bio-hydrogels, to be used as precursor material for constructing novel architectured free-standing carbon electrode materials with well-defined geometry and controlled pore size distribution. The final shape of carbon electrode depends on the 3D geometry of the additive manufactured negative template used for the replication during solvent casting. This technique would broaden the library of hydrogels materials that could be constructed freely in three-dimensions for the fabrication of structured and free-standing porous bio-carbon based electrodes for high-performance supercapacitor application. References [1] Wu, Xi-Lin, and An-Wu Xu. "Carbonaceous hydrogels and aerogels for supercapacitors." Journal of Materials Chemistry A 2, no. 14 (2014): 4852-4864. [2] Li, Huijun, Cavin Tan, and Lin Li. "Review of 3D printable hydrogels and constructs." Materials & Design 159 (2018): 20-38. Acknowledgements The authors greatly acknowledge the funding provided by the European Research Council under the Horizon 2020 framework programme grant no. 772370-PHOENEEX. Figure 1

Narrowly dispersed diblock copolymers containing poly(methyl methacrylate) [PMMA] or poly(nonafluorohexyl methacrylate) [PF9MA] as the first block and poly(ferrocenylmethyl methacrylate) [PFMMA] as the second block, were prepared by anionic polymerization for the first time. Disordered bulk morphologies in the case of PMMA-b-PFMMA were observed and explained in terms of low Flory–Huggins interaction parameter (χ ≤ 0.04). In the case of PF9MA-b-PFMMA hexagonally packed cylinder morphology (HEX) was substantiated from TEM and SAXS observations. Furthermore, high incompatibility between PF9MA and PFMMA blocks allowed for the formation of well-ordered ferrocene containing cylinders on silica substrate upon exposure of the thin films to a saturated solvent vapor. It was shown that the cylinder orientation, parallel or perpendicular to the surface, could easily be controlled by appropriate choice of the solvent and without the need for preliminary surface modification, for example by means of grafted brush layer. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016

The effect of formation and modification methods on the physical properties of polymersomes is critical for their use in applications relying on their ability to mimic functional properties of biological membranes. In this study, we compared two formation methods for polymersomes made from polybutadiene-polyethylene oxide diblock copolymers: detergent-mediated film rehydration (DFR) and solvent evaporation (SE). DFR-prepared polymersomes showed a three times higher permeability compared to SE-prepared polymersomes as revealed by stopped-flow light scattering. SE-prepared polymersomes broke down faster to structures

Nanostructured graphene exhibits many intriguing properties. For example, precisely controlled graphene nanomeshes can be applied in electronic, photonic, or sensing devices. However, fabrication of nanopatterned graphene with periodic supperlattice remains a challenge. In this work, periodic graphene nanomesh was fabricated by photocatalysis of single-layer graphene suspended on top of TiO2-covered nanopillars, which were produced by combining block copolymer nanolithography with atomic layer deposition. Graphene nanoribbons were also prepared by the same method applied to a line-forming block copolymer template. This mask-free and nonchemical/nonplasma route offers an exciting platform for nanopatterning of graphene and other UV-transparent materials for device engineering.

We present a method to make continuous multi-material structures from a monomer solution that becomes a soft hydrogel when exposed to blue light and a hard solid when exposed to UV light. We show that the material can be varied between a hard epoxy material to a several hundred times softer poly(ethylene glycol)-diacrylate material. Moreover, the elastic properties of the material depend on both the wavelength of and exposure time of the light, which is used to produce a material with an elasticity gradient. We expect our material to find use in a range of fields, with immediate applications as 2D sheets with tunable mechanical properties for cell durotaxis studies, and 3D stereolithographically printed tissue mimicks, for example, for disease models and tissue engineering. Spatially resolved photo-polymerization of a mixture of epoxy and acrylate monomers can be used to make multi-material structure, with unique freedom to polymerize each monomer individually. The elastic compressive properties of the material are shown to be fully tunable from 20 MPa depending on the light exposure time. This is used to make a functionally graded continuous material with a large variation in elastic properties. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1195–1201

In our efforts to design an optical sensor for hydrogen peroxide, we have realized the importance of knowing/controlling the diffusion of hydrogen peroxide to the indicator, especially in the case of an irreversible indicator. Since we found little literature data, we decided to test the permeability of hydrogen peroxide in commercially available polymers, focusing on the polyurethanes HydroMed™ and HydroThane™, which are commonly used for immobilization matrices in optical sensors. Measured values are between 5.12 10−9 ± 8.50 10−10 and 2.25 10−6 ± 1.00 10−7 cm2 s−1. Keywords: Hydrogen peroxide, Polymer membrane, Permeability, Diffusivity

We present structural small-angle neutron scattering studies of a three-armed polystyrene star polymer with short deuterated segments at the end of each arm. We show that the form factor of the three-armed star molecules in the relaxed state agrees with that of the random phase approximation of Gaussian chains. Upon exposure to large extensional flow conditions, the star polymers change conformation resulting in a highly stretched structure that mimics a fully extended three-armed tube model. All three arms are parallel to the flow, one arm being either in positive or negative stretching direction, while the two other arms are oriented parallel, right next to each other in the direction opposite to the first arm.

In this work we have performed a detailed analysis of enzymatic degradation of amorphous poly (d, l-lactide) (PDLLA) by measuring the resonance frequencies of polymer coated microcantilevers before and after degradation. The miniaturized cantilever system provides a fast analysis of the biodegradation rate of PDLLA with a minute amount of sample and without the need of thermal and chemical acceleration. The degradation rate of the polymer has been estimated by multilayer cantilever theory and model simulation. A bulk degradation rate of 0.24 μg mm-2 hour-1 is estimated which agrees well with values reported in literature. The role of enzyme concentrations, pre-hydration in buffer, surface morphologies of PDLLA films and adsorption time of enzymes on the rate of degradation has been investigated. An increase in degradation rate is observed with an increase in enzyme concentration and after pre-hydration in buffer. A polymer film with a non-uniform surface degrades faster than the uniform one due to the preference of enzyme attack at film defects. A threshold time of around 3 h is estimated for irreversible enzyme adsorption on the polymer surface after which degradation can proceed even in buffer solution in the absence of enzyme.

A micelle based nanosensor was synthesized and investigated as a ratiometric pH sensor for use in measurements in living cells by fluorescent microscopy. The nanosensor synthesis was based on self-assembly of an amphiphilic triblock copolymer, which was chemically cross-linked after micelle formation. The copolymer, poly(ethylene glycol)-b-poly(2-aminoethyl methacrylate)-b-poly(styrene) (PEG-b-PAEMA-b-PS), was synthesized by isolated macroinitiator atom transfer radical polymerization that forms micelles spontaneously in water. The PAEMA shell of the micelle was hereafter cross-linked by an amidation reaction using 3,6,9-trioxaundecandioic acid cross-linker. The cross-linked micelle was functionalized with two pH sensitive fluorophores and one reference fluorophore, which resulted in a highly uniform ratiometric pH nanosensor with a diameter of 29 nm. The use of two sensor fluorophores provided a sensor with a very broad measurement range that seems to be influenced by the chemical design of the sensor. Cell experiments show that the sensor is capable of monitoring the pH distributions in HeLa cells.

Chemical vapor deposited graphene is nanopatterned by a spherical block-copolymer etch mask. The use of spherical rather than cylindrical block copolymers allows homogeneous patterning of cm-scale areas without any substrate surface treatment. Raman spectroscopy was used to study the controlled generation of point defects in the graphene lattice with increasing etching time, confirming that alongside the nanomesh patterning, the nanopatterned CVD graphene presents a high defect density between the mesh holes. The nanopatterned samples showed sensitivities for NO2 of more than one order of magnitude higher than for non-patterned graphene. NO2 concentrations as low as 300 ppt were detected with an ultimate detection limit of tens of ppt. This is so far the smallest value reported for not UV illuminated graphene chemiresistive NO2 gas sensors. The drastic improvement in the gas sensitivity is believed to be due to the high adsorption site density, thanks to the combination of edge sites and point defect sites. This work opens the possibility of large area fabrication of nanopatterned graphene with extreme density of adsorption sites for sensing applications., Comment: The final publication will be aviable http://www.springer.com/materials/nanotechnology/journal/12274

Metaphase chromosome spreading is the most crucial step required for successful karyotyping and FISH analysis. These two techniques are routinely used in cytogenetics to assess the chromosome abnormalities. The spreading process has been studied for years but it is still considered an art more than a science. The chromosome spreading greatly depends on the environmental conditions such as humidity and temperature, which govern the evaporation of fixative, in which the cells are suspended. The spreading is normally performed manually in ambient conditions on glass slides, which are hydrophilic, and thus allow for better quality spreads. Further cytogenetic analysis depends on the quality of the spreads, which is dependent on the skills of the personnel and is thus limited to laboratory settings. Here, we present a semi-closed microfluidic chip for preparation of the metaphase spreads on a glass and a Topasr substrate rendered more hydrophilic by oxygen plasma treatment coupled with photografting. The device consists of a microfluidic chamber with perfusion holes that facilitate the evaporation of fixative and reliable formation of the spreads. The usability of the chromosome spreads formed on the glass and the Topasr slide is tested by performing FISH analysis.

A modified and improved photografting procedure of Topas® surface hydrophilization is investigated in order to obtain stable modification of the polymer for long term storage. The achieved hydrophilicity and monitoring of the wettability during one month of storage are presented as well as a description of the optimal cleaning procedure and storage conditions to maintain the modified surface. Three minutes of oxygen plasma activation followed by 4 min of acrylic acid UV-photografting at 50 °C leads to the most stable hydrophilicity that was characterized by an initial water contact angle of 53.5° ± 1.2°. Storage of the modified material in cold water at 4 °C and refraining from ultrasonic cleaning limit water contact angle increase to 5° over 30 days. In comparison with pristine hydrophobic Topas, the proposed treatment improves chromosome spreading ability significantly.

We report on the systematic investigation of the optical properties of a selectively grown quantum dot gain material assisted by block-copolymer lithography for potential applications in active optical devices operating in the wavelength range around 1.55 um and above. We investigated a new type of diblock copolymer PS-b-PDMS (polystyrene-block-polydimethylsiloxane) for the fabrication of silicon oxycarbide hard mask for selective area epitaxy of InAs/InP quantum dots. An array of InAs/InP quantum dots was selectively grown via droplet epitaxy. Our detailed investigation of the quantum dot carrier dynamics in the 10-300 K temperature range indicates the presence of a density of states located within the InP bandgap in the vicinity of quantum dots. Those defects have a substantial impact on the optical properties of quantum dots., Comment: 11 pages, 5 figures, 1 table

We compare viscoelastic properties of several polystyrene solutions and melts with the same number of entanglements. It is demonstrated that the modulus and time can be shifted such that the linear viscoelastic properties are identical provided the number of entanglements are identical. However the nonlinear properties in strong extensional flow are different with polymer solutions showing markedly stronger extensional hardening than the corresponding melts. While increased chain extensibility for solutions may provide part of the explanation, it is demonstrated that other mechanisms are needed for a full explanation for the differences between solutions and melts.

In this work we have performed a detailed study of the influence of various parameters on spray coating of polymer films. Our aim is to produce polymer films of uniform thickness (500 nm to 1 μm) and low roughness compared to the film thickness. The coatings are characterized with respect to thickness, roughness (profilometer), and morphology (optical microscopy). Polyvinylpyrrolidone (PVP) is used to do a full factorial design of experiments with selected process parameters such as temperature, distance between spray nozzle and substrate, and speed of the spray nozzle. A mathematical model is developed for statistical analysis which identifies the distance between nozzle and substrate as the most significant parameter. Depending on the drying of the sprayed droplets on the substrate, we define two broad regimes, "dry" and "wet". The optimum condition of spraying lies in a narrow window between these two regimes, where we obtain a film of desired quality. Both with increasing nozzle-substrate distance and temperature, the deposition moves from a wet state to a dry regime. Similar results are also achieved for solvents with low boiling points. Finally, we study film formation during spray coating with poly (D,L-lactide) (PDLLA). The results confirm the processing knowledge obtained with PVP and indicate that the observed trends are identical for spraying of other polymer films.

By a selective complexation between different alkyltrimethylammonium amphiphiles (C8, C12 and C16) and three different diblock copolymer systems of poly(styrene)-b-poly(methacrylic acid) at various grafting densities X (X = number of alkyl chains per acidic group of the poly(methacrylic acid) PMAA block), a class of ionic supramolecules are successfully synthesized whose molecular architecture consists of a poly(styrene) PS block (Linear block) covalently connected to a strongly amphiphilic comb-like block (AmphComb block), i.e. Linear-b-AmphComb. In the melt state, these ionic supramolecules can show simultaneous microphase (between Linear and AmphComb blocks) and nanophase (within the AmphComb blocks) separations. This leads to the formation of various structure-in-structure two-scale hierarchical self-assemblies, including S-in-SLL, S-in-SBCC, S-in-C, S-in-L and C-in-L, where S, SLL, SBCC, C and L stand for spherical, spherical in liquid-like state, spherical in body-centered-cubic arrangement, cylindrical and lamellar, respectively. Synchrotron small angle X-ray scattering (SAXS) and crossed polarizers, together with SAXS modelling analysis, were used for a detailed structural study of the samples. The morphology of the microphase separated state was mapped out on ‘master’ microdomain morphology diagrams as a function of the volume fraction of the AmphComb blocks (ΦAmphComb) and the compositional window of each microdomain morphology was determined. It was observed that, (i) within samples based on the same parent diblock copolymer system, the occurrence of a specific microdomain morphology is only dependent on the value of ΦAmphComb, regardless of the grafting density X and the length of the alkyl side-chains, and (ii) microdomain morphological boundaries occur at ΦAmphComb values of ∼0.20 (SLL/C and SBCC/C) and ∼0.28 (C/L). Finally, the specific influences of the strongly amphiphilic nature of the AmphComb blocks on the observed morphological and hierarchical behaviours of our system are discussed. For reference, stoichiometric strongly amphiphilic comb-like (AmphComb) ionic supramolecules, based on complexation between a homopolymer of PMAA and the various alkyltrimethylammonium amphiphiles, were prepared, which nanophase separated into S (C8) or C (C12 and C16) domains.

We use small-angle neutron scattering (SANS) to study labeled short chains with and without the influence of an entangled and highly stretched surrounding environment of longer chains. We find unequivocal evidence of nematic effects as the blend chains in steady state flow are stretched a factor ∼1.5 more from the presence of the long chain nematic field. In the pure melt we confirm that the nonaffine mean-field result ν=0.5 for the strain coupling is still valid for very fast flows, while in the nematic system our analysis predicts an increased coupling constant. We provide a structural explanation for the two first regimes of the nonlinear relaxation, particularly a transition regime where the long chains are relaxing in a sea of reptating short chains.

Amphiphilic polybutadiene polyethylene oxide (PB-PEO) is one of the best known chemistries to form stable vesicular morphologies, stated as polymersomes, in aqueous environment. Mimicking cell membranes, these structures self-assemble in an “amphiphilic window” determined by 0.15

Due to strong mode-confinement, long propagation-distance, and unique tunability, graphene plasmons have been widely explored in the mid-infrared and terahertz windows. However, it remains a big challenge to push graphene plasmons to shorter wavelengths in order to integrate graphene plasmon concepts with existing mature technologies in the near-infrared region. We investigate localized graphene plasmons supported by graphene nanodisks and experimentally demonstrated graphene plasmon working at 2 {\mu}m with the aid of a fully scalable block copolymer self-assembly method. Our results show a promising way to promote graphene plasmons for both fundamental studies and potential applications in the near-infrared window., Comment: 6 pages, 4 figures, a revised version

We present start-up of uniaxial extension followed by stress relaxation experiments of a bi-disperse 50 % by weight blend of 95k and 545k molecular weight polystyrene. We also show, for comparison, stress relaxation measurements of the polystyrene melts with molecular weight 95k and 545k, which are the components of the bi-disperse melt. The measurements show three separated relaxation regimes: a fast regime, a transition regime, and a slow regime. In the fast regime, the orientation of the long chains is frozen and the stress relaxation is due to stretch relaxation of the short chains primarily. Conversely in the slow regime, the long chains have retracted and undergo relaxation of orientation in fully relaxed short chains.

We use small-angle neutron scattering to measure the molecular stretching in polystyrene melts undergoing steady elongational flow at large stretch rates. The radius of gyration of the central segment of a partly deuterated polystyrene molecule is, in the stretching direction, increasing with the steady stretch rate to a power of about 0.25. This value is about half of the exponent observed for the increase in stress value σ, in agreement with Gaussian behavior. Thus, finite chain extensibility does not seem to play an important role in the strongly non-linear extensional stress behavior exhibited by the linear polystyrene melt.

This study searches for small molecules, which can be generated by photoacid generators (PAGs) capable of inducing the tetragonal-to-monoclinic transformation in zirconia nanocrystals. Metastable tetragonal zirconia nanocrystals were exposed in alcohol suspension. X-ray diffraction analysis showed that water, HCl, HF, and NH3, all initiate phase transformation of tetragonal zirconia at room temperature, whereas NBu4Cl and NBu4OH do not. 2-(4-Methoxystyryl)-4,6- bis(trichloromethyl)-1,3,5-triazine) was the most efficient (monoclinic volume fraction reached 0.57) out of the four tested PAGs. For dispersion in a dimethacrylate matrix together with zirconia crystals, a monoclinic volume fraction of 0.19 was observed after 2 min of exposure to light, increasing to 0.6 after 30 min.

Water is known to initiate a tetragonal to monoclinic phase transformation in zirconia particles. Carbonates on the zirconia surface react with water molecules and hence reduce the transformation rate. This study investigates the possibility of inhibition of the reaction between surface carbonates and water in order to increase the transformation rate in the zirconia crystals. It was found possible to limit the reaction by reacting the surface carbonates with alcohols, a thiol and a primary amide prior to reaction with water. It was also concluded that di- and trialcohols are able to stabilize the tetragonal phase, probably as a result of induced lattice strain.

Particle-based nanosensors have over the past decade been designed for optical fluorescent-based ratiometric measurements of pH in living cells. However, quantitative and time-resolved intracellular measurements of pH in endosomes and lysosomes using particle nanosensors are challenging, and there is a need to improve measurement methodology. In the present paper, we have successfully carried out time-resolved pH measurements in endosomes and lyosomes in living cells using nanoparticle sensors and show the importance of sensor choice for successful quantification. We have studied two nanoparticle-based sensor systems that are internalized by endocytosis and elucidated important factors in nanosensor design that should be considered in future development of new sensors. From our experiments it is clear that it is highly important to use sensors that have a broad measurement range, as erroneous quantification of pH is an unfortunate result when measuring pH too close to the limit of the sensitive range of the sensors. Triple-labeled nanosensors with a pH measurement range of 3.2-7.0, which was synthesized by adding two pH-sensitive fluorophores with different pK(a) to each sensor, seem to be a solution to some of the earlier problems found when measuring pH in the endosome-lysosome pathway.

A problem with dental resin composites is the polymerization shrinkage, which makes the filling loosen from the tooth or induces crack formation. We have developed an expandable metastable tetragonal zirconia filler, which upon reaction with water, is able to counter the polymer shrinkage. The shrinkage of the composite was calculated from density measurements using Archimedes method. The rate of the phase transformation in resin was measured by determining the volume fraction of monoclinic zirconia ( vm). The composite had a vm of 0.5 after 8 h of water storage. The overall shrinkage of the composites was reduced from 3.2% (initially) to 1.7%.

For the first time, the effect of microscale shear stress induced by both mechanical compression and ball-milling on the phase stability of nanocrystalline tetragonal zirconia (t-ZrO 2 ) powders was studied in water free, inert atmosphere. It was found that nanocrystalline t-ZrO 2 powders are extremely sensitive to both macroscopic uniaxial compressive strain and ball-milling induced shear stress and easily transform martensitically into the monoclinic phase. A linear relationship between applied compressive stress and the degree of tetragonal to monoclinic (t → m) phase transformation was observed. Ball-milling induced microscale stress has a similar effect on the t → m phase transformation. Furthermore, it was found that even very mild milling condition, such as 120 rpm, 1 h (0.5 mm balls) was enough to induce phase transformation. Surfactant assisted ball-milling was found to be very effective in de-agglomeration of our nanocrystalline porous ZrO 2 particles into discrete nanocrystals. However, the t → m phase transformation could not be avoided totally even at very mild milling condition. This suggests that the metastable t-ZrO 2 is extreme sensitive to microscale shear stress induced by both mechanical compression and ball-milling. The findings presented in this work are very important in further understanding the stress-induced phase transformation of nanocrystalline t-ZrO 2 powders in a water free atmosphere and their further stabilization in industrially relevant solvents.

This work highlights an attempt to characterize the degree and nature of long-chain branching (LCB) in an unknown sample of ethylene-propylene-diene rubber (EPDM). Two EPDM rubbers selected for this study were comparable in comonomer compositions but significantly different with respect to molar mass and the presence of LCB. Both rubbers contained 5-ethylidene-2-norbornene (ENB) as diene. Solution cast films of pure EPDM samples were used for different characterization techniques. 1H-NMR, and 13C-NMR were used for assessing the comonomer ratios and LCB. Size exclusion chromatography (SEC) equipped with triple detector system was used to determine the molar mass (both absolute and relative) and polydispersity index (PDI). Presence of branching was also detected using sec-viscometry. Rheological analysis has also been used for characterizing LCB. Finally, on the basis of the experimental findings and the available theories, an attempt was made to identify the chemical nature and degree of LCB. This study reveals the possibility of detailed characterization of molecular architecture of EPDM containing LCB by comparing with an essentially linear EPDM in light of an existing theory. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Phosphate sensors were developed by embedding fluorescent reporter proteins (FLIPPi) in polyacrylamide nanoparticles with diameters from 40 to 120 nm. The sensor activity and protein loading efficiency varied according to nanoparticle composition, that is, the total monomer content (% T) and the cross-linker content (% C). Nanoparticles with 28% T and 20% C were considered optimal as a result of relatively high loading efficiency (50.6%) as well as high protein activity (50%). The experimental results prove that the cross-linked polyacrylamide matrix could protect FLIPPi from degradation by soluble proteases to some extent. This nanoparticle embedding method provides a novel promising tool for in vivo metabolite studies. It also demonstrates a universal method for embedding different fragile bioactive elements, such as antibodies, genes, enzymes, and other functional proteins, in nanoparticles for, for example, sensing, biological catalysis, and gene delivery.

In this study, the physical affinity between an epoxy matrix and oxidized, unsized carbon fibers has been evaluated using Hansen solubility (cohesion) parameters (HSP). A strong physical compatibility has been shown, since their respective HSP are close. The use of a glassy carbon substrate as a model for unsized carbon fiber has been demonstrated as appropriate for the study of interactions between the materials in composite carbon fiber–epoxy systems. The HSP of glassy carbon are similar to those of carbon fibers and epoxy matrix.

Through mixing isotactic-polypropylene (i-PP) and atactic-polypropylene (a-PP), we have demonstrated the importance of the crystallinity in polypropylene as an electret material. Samples with crystallinities between 7 % and 47 % were used. A high degree of crystallinity in polypropylene, used as an electret, gives a better charge stability with respect to temperature and humidity changes. The semicrystalline i-PP significantly outperforms a-PP regarding charge stability. a-PP is an amorphous polymer. By mixing a-PP and i-PP, the degree of crystallinity can be controlled, while all other sample preparation processes and characteristics can be identical. This is important since the performance of an electret material is sensitive to its previous process history. Activation energies used for predicting the thermal potential decay are determined from thermally stimulated current and isothermal potential decay experiments. Activation energies from 0.98 eV to 1.41 eV were determined. From these values, a very good agreement was achieved between the experimental potential decay at room temperature for more than 290 days, and a theoretical estimation of the potential decay.

The work elucidates the feasibility of incorporation of phosphorus-silicon containing fire retardant (10-(2-trimethoxysilylethyl)- 9-hydro-9-oxa-10-phosphaphenanthrene-10-oxide [DOPO-VTS]) into nanosol coating solutions by cohydrolysis cocondensation reaction of DOPO-VTS with tetraethoxysilane precursor (TEOS). Impregnation of cotton with the organophosphorus silane in a form of nanosol dispersion afforded better fire retardancy of such samples compared to pure DOPO or TEOS-treated cotton indicating synergism between phosphorus and silicon containing species in a condensed phase. The detailed analysis by TGA-MS and SEM pointed to the fact that DOPO-VTS acts as a promoter of cotton degradation which, in turn, results in acceleration of the charring process and formation of compact char in contrast to TEOS-treated samples. Further analysis of the char by XPS confirmed high content of carbonaceous residue in the case of DOPO-VTS-treated samples while mainly siliceous component was left in the char in case of cotton treated with TEOS. Standard flammability test (EN ISO 15025:2008) additionally confirmed the absence of smoldering and better overall fire performance of the DOPO-VTS samples in contrast to TEOS-treated samples.

Micromechanical string resonators are used as a highly sensitive tool for the detection of glass transition (Tg or α relaxation) and sub-Tg (β relaxation) temperatures of polystyrene (PS) and poly (methyl methacrylate) (PMMA). The characterization technique allows for a fast detection of mechanical relaxations of polymers with only few nanograms of sample in a quasi-static condition. The polymers are spray coated on one side of silicon nitride (SiN) microstrings. These are pre-stressed suspended structures clamped on both ends to a silicon frame. The resonance frequency of the microstrings is then monitored as a function of increasing temperature. α and β relaxations in the polymer affect the net static tensile stress of the microstring and result in measureable local frequency slope maxima. Tg of PS and PMMA is detected at 91 ±2°C and 114 ±2°C, respectively. The results match well with the glass transition values of 93.6°C and 114.5°C obtained from differential scanning calorimetry of PS and PMMA, respectively. The β relaxation temperatures are detected at 30 ± 2°C and 33 ± 2°C for PS and PMMA which is in accordance with values reported in literature. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 1035–1039

Selecting the appropriate analytical methods for characterizing the assembly and morphology of polymer-based vesicles, or polymersomes are required to reach their full potential in biotechnology. This work presents and compares 17 different techniques for their ability to adequately report size, lamellarity, elastic properties, bilayer surface charge, thickness and polarity of polybutadiene-polyethylene oxide (PB-PEO) based polymersomes. The techniques used in this study are broadly divided into scattering techniques, visualization methods, physical and electromagnetical manipulation and sorting/purification. Of the analytical methods tested, Cryo-transmission electron microscopy and atomic force microscopy (AFM) turned out to be advantageous for polymersomes with smaller diameter than 200 nm, whereas confocal microscopy is ideal for diameters >400 nm. Polymersomes in the intermediate diameter range can be characterized using freeze fracture Cryo-scanning electron microscopy (FF-Cryo-SEM) and nanoparticle tracking analysis (NTA). Small angle X-ray scattering (SAXS) provides reliable data on bilayer thickness and internal structure, Cryo-TEM on multilamellarity. Taken together, these tools are valuable for characterizing polymersomes per se but the comparative overview is also intended to serve as a starting point for selecting methods for characterizing polymersomes with encapsulated compounds or polymersomes with incorporated biomolecules (e.g. membrane proteins).

In recent years, aquaporin biomimetic membranes (ABMs) for water separation have gained considerable interest. Although the first ABMs are commercially available, there are still many challenges associated with further ABM development. Here, we discuss the interplay of the main components of ABMs: aquaporin proteins (AQPs), block copolymers for AQP reconstitution, and polymer-based supporting structures. First, we briefly cover challenges and review recent developments in understanding the interplay between AQP and block copolymers. Second, we review some experimental characterization methods for investigating AQP incorporation including freeze-fracture transmission electron microscopy, fluorescence correlation spectroscopy, stopped-flow light scattering, and small-angle X-ray scattering. Third, we focus on recent efforts in embedding reconstituted AQPs in membrane designs that are based on conventional thin film interfacial polymerization techniques. Finally, we describe some new developments in interfacial polymerization using polyhedral oligomeric silsesquioxane cages for increasing the physical and chemical durability of thin film composite membranes.

An elaborate survey of the chemical modification methods for endowing highly flammable SBS with increased fire resistant properties by means of chemical modification of the polymer backbone with phosphorus containing fire retardant species is presented. Optimal conditions for free radical addition of the P H containing fire retardants to a double bonds of poly(butadiene) block of SBS were found, affording varied degree of the modification (0.2–21 mol%). Alternatively, a two-step procedure based on an epoxidation step followed by hydrolysis of the epoxides with phosphoric acid was developed resulting in 20 mol% of poly(butadiene) block modification. Based on TGA results, organophosporus-modified SBS was found to be amenable to charring – a property which correlated directly with the reduced flammability of the modified polymer observed in Cone Calorimetry tests. Furthermore, conceptually novel application of the H3PO4 modified SBS as a fire retardant additive for bitumen material, in combination with synergetic melamine species, offered 25% better self-extinguishing properties of such formulation already at a low loading level of the fire retardant components (3.5 wt.%).